A refractory material for a glass melting furnace resistant to water vapor and a method of manufacturing the same

Abstract

The application belongs to the technical field of refractory materials, and particularly relates to a water-vapor-resistant refractory material for a glass melting furnace and a preparation method. The method uses modified electrofusion magnesium-aluminum spinel, modified nano-titanium dioxide, aluminum titanate, scandium oxide stabilized zirconia, nano-silicon carbide, nano-aluminum oxide, zirconite micro powder and polyvinyl alcohol solution as raw materials to prepare the water-vapor-resistant refractory material for the glass melting furnace. The material has high thermal shock resistance, high corrosion resistance and low thermal conductivity, and can effectively improve the use efficiency of the glass furnace.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of refractory materials, and particularly relates to a water-vapor-resistant refractory material for a glass melting furnace and a preparation method. BACKGROUND

[0002] The production of glass relies on the high-temperature melting of quartz sand and soda ash and other raw materials in a glass furnace, which poses severe challenges to the refractory materials used in the glass furnace, including withstanding high temperatures, corrosion, and thermal conductivity rates. Although existing refractory materials perform well in terms of strength and corrosion resistance, they lack thermal shock resistance when faced with dramatic temperature changes, and are prone to cracking when the temperature changes rapidly, affecting their service life. When the refractory material is chemically corroded by molten glass, it is prone to chemical erosion, leading to a gradual decline in material performance and increasing the maintenance cost of the glass furnace. Many refractory materials also have the problem of excessively high thermal conductivity, which can cause rapid heat transfer, increasing energy consumption and reducing thermal efficiency. Therefore, it is an urgent need to develop a refractory material with stronger thermal shock resistance, corrosion resistance, and low thermal conductivity to improve the efficiency of the glass furnace. SUMMARY

[0003] Therefore, the purpose of the present application is to overcome the above technical deficiencies and provide a water-vapor-resistant refractory material for a glass melting furnace and a preparation method. The refractory material prepared by the method has stronger thermal shock resistance, corrosion resistance, and low thermal conductivity.

[0004] In a first aspect, the technical solution adopted by the present application to solve the above technical problems is:

[0005] A water-vapor-resistant refractory material for a glass melting furnace, the refractory material comprises, by weight: modified fused magnesium aluminate spinel 15-20 parts, modified nano-titanium dioxide 5-8 parts, aluminum titanate 15-20 parts, scandium oxide stabilized zirconia 10-15 parts, nano-silicon carbide 10-15 parts, nano-alumina 5-10 parts, zirconite micro powder 10-20 parts, and polyvinyl alcohol solution 3-5 parts.

[0006] Further, the preparation method of the modified fused magnesium aluminate spinel is as follows: 14g of flake graphite, 2.5g of Al-Si alloy powder, and 2g of sodium tripolyphosphate are placed in a ball mill jar, mixed for 30min, 83.5g of fused magnesium aluminate spinel is added, and mixed in a high-speed mixer for 20min, 8.5g of phenolic resin and 0.6g of urotropine are then mixed for 15min, and the mixture is placed in a 60℃ vacuum drying oven for drying until the volatile matter content is controlled between 0.85% and 0.95%, obtaining the modified fused magnesium aluminate spinel.

[0007] Further, the preparation method of the modified nano-titanium dioxide: 170 mL of tetrabutyl titanate is slowly added into 830 mL of anhydrous ethanol, and then 1.86 g of ferrocene is added, and the addition of tetrabutyl titanate and ferrocene is completed on a magnetic stirrer until stirring is uniform, to obtain solution A; in a flame spray pyrolysis reactor FSP, the gas flow is adjusted to be H 25.3 L / min, O 25.0 L / min, and air 11.9 L / min, respectively, and solution A is delivered at 5.0 mL / min, and then combustion is performed in a hydrogen-oxygen flame after ignition, to prepare the modified nano-titanium dioxide.

[0008] In a second aspect, the present application provides a preparation method of a refractory material for a glass melting furnace resistant to water vapor, the preparation method comprising the following steps:

[0009] S1, weighing the raw materials in the above technical solution by weight parts, for standby;

[0010] S2, putting the modified electrofusion magnesium-aluminum spinel, modified nano-titanium dioxide, aluminum titanate, scandium oxide stabilized zirconia, nano-silicon carbide, nano-alumina, and zirconite powder weighed in step S1 into a ball mill and mixing uniformly, adding polyvinyl alcohol solution and thoroughly mixing uniformly in a low-speed mixing stirrer, to obtain a mixture;

[0011] S3, under the condition of 120 MPa, pouring the mixture into an isostatic press for compression molding, drying, to obtain a green body;

[0012] S4, heat treating the green body at 1600-1800℃ for 6-8h, to obtain the final refractory material.

[0013] Preferably, the rotation speed of the raw materials in step S2 of the present application is 300 rpm when mixing in the ball mill, and the time is 1-3h.

[0014] Preferably, the mixture needs to be aged for 3-4h after mixing uniformly in step S2 of the present application. Aging is to make the raw materials mix more uniformly, which is crucial to ensure the uniform structure and performance of the refractory material.

[0015] Preferably, the drying temperature in step S3 of the present application is 150℃, and the time is 6h.

[0016] Preferably, the drying in step S3 of the present application is followed by room temperature curing for 20-24h. The purpose of room temperature curing is to improve the structural stability of the material, to ensure the durability in the subsequent use process.

[0017] Preferably, the heating rate in step S4 of the present application is 4℃ / min, and the cooling rate is 3℃ / min.

[0018] Preferably, the step S4 heat treatment process is carried out under nitrogen protection.

[0019] The present application has the following beneficial effects:

[0020] 1、The modified fused magnesium aluminum spinel in the present application has significant advantages in performance, mainly in corrosion resistance, high temperature resistance, thermal shock stability, and mechanical properties. By introducing ingredients such as sodium tripolyphosphate and boron glass powder, the modified fused magnesium aluminum spinel improves its corrosion resistance to high-temperature molten glass and other corrosive media, inhibits material surface corrosion and structural degradation caused by chemical reactions in high-temperature environments, and prolongs the service life of the material. The addition of flake graphite and Al-Si alloy powder improves the stability of the material under extreme high-temperature conditions, reduces crack generation and propagation caused by thermal stress, improves the thermal shock resistance of the material, and ensures the long-term reliability of the material in a working environment with large temperature fluctuations. And the modified fused magnesium aluminum spinel crystal framework is very tight and stable, so that the material can still maintain structural integrity in high-temperature and water vapor environments. Therefore, the modified spinel also has good water vapor resistance. The modified fused magnesium aluminum spinel is optimized in terms of high temperature, corrosion, water vapor resistance, and thermal shock resistance, making it an ideal refractory raw material for glass kilns and other high-temperature, harsh working conditions, meeting the higher performance requirements of modern industry for refractory raw materials.

[0021] 2、The advantages of the modified nano-titanium dioxide in the present application mainly include: iron doping can effectively adjust the electronic structure of nano-titanium dioxide, promote the improvement of its catalytic activity and thermal stability. In refractory materials, iron-doped nano-titanium dioxide enhances the thermal shock resistance of the material, improves its corrosion resistance and mechanical strength in high-temperature environments. This doping modification enables the material to maintain better structural stability under extreme temperature changes, reduces crack propagation and rupture caused by thermal stress, and improves the durability of the material in high-temperature, strongly corrosive media. Therefore, the addition of modified nano-titanium dioxide effectively improves the comprehensive performance of refractory materials and expands their application prospects in high-temperature industrial applications. BRIEF DESCRIPTION OF DRAWINGS

[0022] Fig. 1 is a comparison chart of the thermal shock resistance of the refractory materials in Example 1-3 group and Comparative Example 1-3 group.

[0023] Fig. 2 is a comparison chart of the thermal conductivity of the refractory materials in Example 1-3 group and Comparative Example 1-3 group.

[0024] Fig. 3 is a comparison chart of the corrosion resistance of the refractory materials in Example 1-3 group and Comparative Example 1-3 group. DETAILED DESCRIPTION

[0025] The present application is explained by specific examples below, and other advantages and effects of the present application can be easily understood by those skilled in the art from the disclosure of the specification. The present application can also be implemented or applied by other different specific embodiments, and various modifications or changes can be made based on different views and applications without departing from the spirit of the present application. It should be noted that the following examples and features in the examples can be combined with each other without conflict. The electrically fused magnesium-aluminum spinel is purchased from Henan Fengkai Refractory Material Co., Ltd., the tetrabutyl titanate is purchased from Shandong Huayao Biological Technology Co., Ltd., the ferrocene is purchased from Shandong Mao Fa Chemical Co., Ltd., the flake graphite is purchased from Lingshou County Shifeng Mining Processing Factory, the Al-Si alloy powder is purchased from Hengbei Metal Material Co., Ltd., the sodium tripolyphosphate is purchased from Shandong Jinyou Biological Technology Co., Ltd., the urotropine is purchased from Jiaozuo Runhua Chemical Industry Co., Ltd., the phenolic resin is purchased from Henan Ptun New Material Co., Ltd., the scandium oxide stabilized zirconia is purchased from Shanghai Mingjia Trade Co., Ltd., the nano silicon carbide is purchased from Wuhan Lana Bai Pharmaceutical and Chemical Co., Ltd., and the nano alumina is purchased from Zhuotai New Material Technology Co., Ltd.

[0026] Example 1

[0027] The present embodiment provides a water vapor resistant refractory material for a glass melting furnace and a preparation method, and the specific steps are as follows:

[0028] S1, accurately weigh the modified electrically fused magnesium-aluminum spinel 15 parts, the modified nano titanium dioxide 5 parts, the aluminum titanate 15 parts, the scandium oxide stabilized zirconia 10 parts, the nano silicon carbide 10 parts, the nano alumina 5 parts, the micro powder of zirconite 10 parts, and the polyvinyl alcohol solution 3 parts with a balance, and reserve them;

[0029] The preparation process of the modified electrically fused magnesium-aluminum spinel is as follows: 14 g of flake graphite, 2.5 g of Al-Si alloy powder, and 2 g of sodium tripolyphosphate are put into a ball mill tank and mixed for 30 min, then 83.5 g of electrically fused magnesium-aluminum spinel is added, transferred to a high-speed mixer for mixing for 20 min, then 8.5 g of phenolic resin and 0.6 g of urotropine are added and mixed for 15 min, and the mixture is placed in a 60℃ vacuum drying oven for drying until the volatile matter content is controlled at about 0.85%, to obtain the modified electrically fused magnesium-aluminum spinel.

[0030] The preparation process of the modified nanometer titanium dioxide is as follows: a beaker is taken, 830 mL of anhydrous ethanol is added, the beaker containing the ethanol is placed on a magnetic stirrer, 170 mL of tetrabutyl titanate is slowly added dropwise under the action of the magnetic stirrer, 1.86 g of ferrocene is further added, and after uniform stirring, solution A is prepared; in a flame spray pyrolysis reactor FSP (purchased from Shanghai Fuguang Precision Instrument Co., Ltd.), the gas flow is adjusted, and is respectively set as: H2 5.3 L / min, O2 5.0 L / min, air 11.9 L / min, and solution A is delivered at 5.0 mL / min, ignition is performed in the hydrogen-oxygen flame, and the modified nanometer titanium dioxide is prepared.

[0031] S2, the modified fused magnesium aluminum spinel, the modified nanometer titanium dioxide, the aluminum titanate, the scandium oxide stabilized zirconia, the nanometer silicon carbide, the nanometer aluminum oxide and the zirconite powder weighed in step S1 are put into a ball mill for mixing at a speed of 300 rpm for 1 h, and then a polyvinyl alcohol solution is added and thoroughly mixed in a low-speed mixing stirrer, and the material is mixed for 3 h to obtain a mixture;

[0032] S3, the mixture is poured into an isostatic press, and is pressed and formed under the condition of 120 MPa, and then is placed in a drying machine for drying at 150℃ for 6 h and solidification at room temperature for 20 h to obtain a green body of the refractory material suitable for a glass furnace;

[0033] S4, the green body is placed in a high-temperature tunnel kiln, and is heated to 1600℃ at a heating rate of 4℃ / min, is kept at 1600℃ for 6 h, and is then cooled to room temperature at a cooling rate of 3℃ / min to obtain the final water vapor resistant refractory material for a glass melting furnace.

[0034] Example 2

[0035] The embodiment provides a preparation method of a water vapor resistant refractory material for a glass melting furnace, and the specific steps are as follows:

[0036] S1, the modified fused magnesium aluminum spinel 17 parts, the modified nanometer titanium dioxide 6 parts, the aluminum titanate 17 parts, the scandium oxide stabilized zirconia 12 parts, the nanometer silicon carbide 12 parts, the nanometer aluminum oxide 7 parts, the zirconite powder 15 parts and the polyvinyl alcohol solution 4 parts are accurately weighed by a balance and prepared for use;

[0037] The preparation process of the modified fused magnesium aluminum spinel is as follows: 14 g of flake graphite, 2.5 g of Al-Si alloy powder and 2 g of sodium tripolyphosphate are put into a ball mill jar and mixed for 30 min, 83.5 g of fused magnesium aluminum spinel is further added, is transferred to a high-speed mixer for mixing for 20 min, 8.5 g of phenolic resin and 0.6 g of urotropine are further added and mixed for 15 min, and then the mixture is placed in a 60℃ vacuum drying box for drying until the volatile content is controlled at about 0.90%, to obtain the modified fused magnesium aluminum spinel.

[0038] The preparation process of the modified nanometer titanium dioxide is as follows: a beaker is taken, 830 mL of anhydrous ethanol is added, the beaker containing the ethanol is placed on a magnetic stirrer, 170 mL of tetrabutyl titanate is slowly added dropwise under the action of the magnetic stirrer, and then 1.86 g of ferrocene is added. After stirring uniformly, solution A is prepared. In a flame spray pyrolysis reactor FSP (purchased from Shanghai Fuguang Precision Instrument Co., Ltd.), the gas flow is adjusted to be H2 5.3 L / min, O2 5.0 L / min, and air 11.9 L / min, respectively, and solution A is delivered at a rate of 5.0 mL / min. After ignition, the modified nanometer titanium dioxide is prepared by burning in the hydrogen-oxygen flame.

[0039] S2, the modified fused magnesium aluminum spinel, modified nanometer titanium dioxide, aluminum titanate, scandium oxide stabilized zirconia, nanometer silicon carbide, nanometer aluminum oxide, and zirconite powder weighed in step S1 are put into a ball mill for mixing at a speed of 300 rpm for 2 h, and then polyvinyl alcohol solution is added and thoroughly mixed in a low-speed mixing stirrer. The mixture is mixed for 3.5 h to obtain a mixed material;

[0040] S3, the mixed material is poured into an isostatic press and pressed into a shape under the condition of 120 MPa. After shaping, it is placed in a drying machine and dried at 150°C for 6 h, and then solidified at room temperature for 22 h to obtain a green body of the refractory material suitable for a glass furnace;

[0041] S4, the green body is placed in a high-temperature tunnel kiln, and the temperature is raised to 1600°C at a rate of 4°C / min. After holding at 1600°C for 6 h, the temperature is lowered to room temperature at a rate of 3°C / min to obtain the final water vapor resistant refractory material for a glass melting furnace.

[0042] Example 3

[0043] The present embodiment provides a preparation method of a water vapor resistant refractory material for a glass melting furnace, and the specific steps are as follows:

[0044] S1, accurately weigh 20 parts of modified fused magnesium aluminum spinel, 8 parts of modified nanometer titanium dioxide, 20 parts of aluminum titanate, 15 parts of scandium oxide stabilized zirconia, 15 parts of nanometer silicon carbide, 10 parts of nanometer aluminum oxide, 20 parts of zirconite powder, and 5 parts of polyvinyl alcohol solution using a balance, and reserve them for use;

[0045] The preparation process of the modified fused magnesium aluminum spinel is as follows: 14 g of flake graphite, 2.5 g of Al-Si alloy powder, and 2 g of sodium tripolyphosphate are put into a ball mill jar and mixed for 30 min, 83.5 g of fused magnesium aluminum spinel is then added, and the mixture is transferred to a high-speed mixer for mixing for 20 min. 8.5 g of phenolic resin and 0.6 g of urotropine are then added and mixed for 15 min. The mixture is placed in a vacuum drying oven at 60°C for drying until the volatile content is controlled at about 0.95%. The modified fused magnesium aluminum spinel is obtained.

[0046] The preparation process of the modified nanometer titanium dioxide is as follows: a beaker is taken, 830 mL of anhydrous ethanol is added, the beaker containing the ethanol is placed on a magnetic stirrer, 170 mL of tetrabutyl titanate is slowly added dropwise under the action of the magnetic stirrer, 1.86 g of ferrocene is added, and after stirring uniformly, solution A is prepared; in a flame spray pyrolysis reactor FSP (purchased from Shanghai Fuguan Precision Instrument Co., Ltd.), the gas flow is adjusted, and is set as H2 5.3 L / min, O2 5.0 L / min and air 11.9 L / min respectively, and solution A is delivered at 5.0 mL / min, and the modified nanometer titanium dioxide is prepared by burning in the hydrogen-oxygen flame after ignition.

[0047] S2, the modified fused magnesium aluminum spinel, the modified nanometer titanium dioxide, the aluminum titanate, the scandium oxide stabilized zirconia, the nanometer silicon carbide, the nanometer aluminum oxide and the zirconite micropowder weighed in step S1 are put into a ball mill for mixing at a speed of 300 rpm for 3 h, and then a polyvinyl alcohol solution is added and thoroughly mixed and stirred in a low-speed mixing stirrer, and the material is kept for 4 h to obtain a mixture;

[0048] S3, the mixture is poured into an isostatic pressing machine and pressed under the condition of 120 MPa to form a shape, and then the formed shape is placed in a drying machine and dried at 150°C for 6 h and solidified at room temperature for 24 h to obtain a green body of the refractory material suitable for a glass kiln;

[0049] S4, the green body is placed in a high-temperature tunnel kiln, the temperature is raised to 1600°C at a rate of 4°C / min, kept at 1600°C for 6 h, and then the temperature is lowered to room temperature at a rate of 3°C / min to obtain the final glass melting furnace refractory material resistant to water vapor.

[0050] Comparative Example 1: Compared with Example 2, in the raw material components, the fused magnesium aluminum spinel is not modified, and the fused magnesium aluminum spinel is directly added, and the rest refers to Example 2.

[0051] Comparative Example 2: Compared with Example 2, in the raw material components, the nanometer titanium dioxide is not modified, and the nanometer titanium dioxide is directly added, and the rest refers to Example 2.

[0052] Comparative Example 3: Compared with Example 2, in the raw material components, the scandium oxide stabilized zirconia is replaced by zirconia, and the rest refers to Example 2.

[0053] The refractory materials prepared in Examples 1-3 and Comparative Examples 1-3 are tested for related properties.

[0054] Physical property test: bulk density is the ratio of the mass of the material to the total volume of the material, and apparent porosity is the percentage of the volume of all open pores in the material to the total volume of the material. Bulk density and apparent porosity are key physical performance indicators of refractory materials. The test results are obtained according to GB / T 2997-2000 "Test method for bulk density, apparent porosity and true porosity of dense shaped refractory products".

[0055] Mechanical property test: cold crushing strength is an important indicator of the mechanical properties of refractory materials, which measures the limit stress of refractory materials under the action of pressure load at room temperature. It can reflect the compressive capacity of the material at room temperature. The cold crushing strength of the sample is tested according to the national standard GB / T 5072-2023 "Test method for cold crushing strength of refractory materials". The flexural strength is another important indicator of the mechanical properties of the material, which measures the ability of refractory materials to resist breaking when subjected to bending force. It reflects the structural integrity and durability of the material in a high-temperature environment. The high-temperature flexural strength of the sample is tested according to the national standard GB / T 3002-2004 "Test method for high-temperature flexural strength of refractory materials".

[0056] High-temperature performance test: load softening temperature is an indicator of the ability of refractory materials to resist deformation under the combined action of high temperature and load. It reflects the structural strength of the material in a high-temperature environment. In this paper, the test is carried out according to the standard GB / T 5989-2023 "Test method for load softening temperature of refractory materials by differential temperature rise method".

[0057] Thermal shock resistance test: thermal shock resistance refers to the ability of refractory materials to resist crack generation and propagation under rapid temperature changes. It is a comprehensive performance of the mechanical and thermal properties of the material under temperature changes. The specific operation method is to place the sample in a 1100℃ electric furnace for 20min, take out the sample and let it cool naturally to room temperature, measure the cold flexural strength of the sample after thermal shock, calculate the residual strength retention rate, and use it to evaluate the thermal shock resistance of the sample. The calculation formula is: residual strength retention rate (%) = residual cold flexural strength / original cold flexural strength x 100%.

[0058] Corrosion resistance test: corrosion resistance refers to the ability of refractory materials to resist chemical corrosion, such as oxidation, sulfidation, nitridation and other corrosion forms in high temperature environment, which is crucial to the stability of materials in high temperature complex corrosive environment. According to the national standard GB / T 14983-2008 "refractory alkali resistance test method", the sample is cut into a nearly square particle with side length of 3-5mm and dried in a drying oven; the potassium carbonate and nano carbon black are mixed uniformly according to the mass ratio of 1:1 as the corrosion medium; the corrosion medium with the same mass as the sample to be corroded is put into a graphite crucible and compacted, a stainless steel mesh support is placed on the top to support the sample, and the sample to be corroded is placed on the support, ensuring that the crucible cover is tightly screwed and then rotated in the opposite direction for two turns; the graphite crucible containing the sample and the corrosion medium is placed in a corundum box, covered with coke, and then placed in an electric furnace at 1000℃ for 10h, and then naturally cooled to room temperature. The mass of the sample before and after alkali corrosion is recorded, and the mass increase rate is calculated to evaluate the corrosion resistance of the sample: the calculation formula is: mass increase rate (%) = (mass of the sample after alkali resistance test - mass of the sample before alkali resistance test) / mass of the sample before alkali resistance test x 100%.

[0059] Thermal conductivity test: thermal conductivity (also known as thermal conductivity) refers to the heat passing through the vertical area per unit time under unit temperature gradient, which is an important physical index to characterize the thermal conductivity of refractory materials. According to the national standard GB / T 36133-2018 "refractory thermal conductivity test method (platinum resistance thermometer method)", the sample is heated to the set temperature in a muffle furnace, and local heating is carried out by embedding linear conductors (heat wires) along the length direction of the sample. These heat wires transmit current at constant power, and the power in the length direction of the sample remains unchanged for a certain time. By measuring the power, current and temperature change after a certain time interval, the thermal conductivity of the material is calculated. The calculation formula is as follows:

[0060]

[0061] In the formula, λ is the thermal conductivity;

[0062] I is the heating current;

[0063] V is the voltage at both ends of the heat wire;

[0064] L is the length of the heat wire;

[0065] t1, t2 are the measured times after the heating current is turned on;

[0066] θ1, θ2 are the temperatures of the heat wire at t1 and t2.

[0067] Table 1

[0068]

[0069] The test results are shown in Table 1. Figs. 1 to 3 As can be seen from Table 1, in the normal temperature pressure strength test, high temperature bending strength test, load softening temperature test and apparent porosity test: the performance of the Example 1-3 groups is better than that of the Comparative Example 1-3 groups in various performance indicators; among them, the refractory material of the Example 2 group shows the best performance in all aspects.

[0070] In the thermal shock resistance performance test: the residual strength retention rate of the Example 1-3 groups is significantly higher than that of the Comparative Example 1-3 groups, among which the residual strength retention rate of the Example 2 group is the highest. The residual strength retention rate is an important indicator for measuring the thermal shock resistance of materials, reflecting the proportion of strength that the material can maintain after being subjected to thermal shock. The material with good thermal shock resistance has a higher residual strength retention rate after experiencing rapid temperature changes, indicating that the thermal shock resistance of the Example 1-3 groups is significantly higher than that of the Comparative Example 1-3 groups, and the thermal shock resistance of the Example 2 group is the best.

[0071] In the corrosion resistance performance test: the mass increase rate of the Example 1-3 groups is significantly lower than that of the Comparative Example 1-3 groups, among which the mass increase rate of the Example 2 group is the lowest. Since the lower the mass increase rate, the higher the stability of the material in the corrosion medium, the better the corrosion resistance of the material, indicating that the corrosion resistance of the Example 1-3 groups is better than that of the Comparative Example 1-3 groups, and the corrosion resistance of the Example 2 group is the best.

[0072] In the thermal conductivity test: the thermal conductivity coefficient of the Example 1-3 groups is significantly lower than that of the Comparative Example 1-3 groups, among which the thermal conductivity coefficient of the Example 2 group is the lowest. Since the thermal conductivity coefficient and the thermal conductivity are different names for the same physical quantity, both of which are used to describe the heat transfer capacity of the material per unit area per unit time under a unit temperature gradient, indicating that the thermal conductivity of the Example 1-3 groups is lower than that of the Comparative Example 1-3 groups, and the thermal conductivity of the Example 2 group is the lowest, with the lowest energy consumption.

[0073] As can be seen, the synergistic effect of modified electro-fused magnesium-aluminum spinel, modified nano-titanium dioxide, scandium oxide stabilized zirconium oxide and other raw material components enables the prepared refractory material to exhibit significant advantages in multiple performance indicators. The composite effect of these components not only significantly improves the thermal shock resistance and corrosion resistance of the material, ensuring its long-term stability and structural integrity in high-temperature environments, but also reduces the thermal conductivity of the material, reduces heat damage and maintenance costs, and improves safety and production efficiency. Through this composite modification, the refractory material can more effectively cope with extreme temperature changes and corrosion of corrosive media in actual application, thereby improving overall production efficiency and prolonging the service life of the material.

[0074] The above embodiments only express the specific implementation of the present application, which is described in more detail and in more detail, but cannot be understood as a limitation on the protection scope of the present application. It should be noted that for ordinary skilled persons in the art, any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application are equivalent replacement methods and are included in the protection scope of the present application.

Claims

1. A refractory material for a glass melting tank resistant to water vapor, characterized by: The refractory material comprises, by weight: modified fused magnesia-alumina spinel 15-20 parts, modified nano-titania 5-8 parts, aluminum titanate 15-20 parts, scandium oxide stabilized zirconia 10-15 parts, nano-silicon carbide 10-15 parts, nano-alumina 5-10 parts, zirconite micro powder 10-20 parts, polyvinyl alcohol solution 3-5 parts; the preparation method of the modified fused magnesia-alumina spinel is: 14 g of flake graphite, 2.5 g of Al-Si alloy powder and 2 g of sodium tripolyphosphate are put into a ball mill jar, mixed for 30 min, then 83.5 g of fused magnesia-alumina spinel is added, and mixed again in a high-speed mixer for 20 min, then 8.5 g of phenolic resin and 0.6 g of urotropine are mixed for 15 min, and dried to obtain the modified fused magnesia-alumina spinel; the preparation method of the modified nano-titania is: 170 mL of tetrabutyl titanate is slowly added to 830 mL of anhydrous ethanol, then 1.86 g of ferrocene is added, and the addition process is completed on a magnetic stirrer until the stirring is uniform, to obtain solution A; in a flame pyrolysis reactor, hydrogen is set to 5.3 L / min, oxygen is set to 5.0 L / min, air is set to 11.9 L / min, and solution A is delivered at 5.0 mL / min, and after ignition, the modified nano-titania is prepared by burning in the hydrogen-oxygen flame.

2. A method of making a water vapor resistant refractory for a glass melter as defined in claim 1, characterized in that: The specific preparation steps of the material are as follows: S1, the raw materials are weighed according to the weight parts in claim 1, and are ready for use; S2, the modified fused magnesia-alumina spinel, the modified nano-titania, the aluminum titanate, the scandium oxide stabilized zirconia, the nano-silicon carbide, the nano-alumina and the zirconite micro powder are put into a ball mill and mixed uniformly, and the polyvinyl alcohol solution is added and thoroughly mixed in a low-speed mixing stirrer to obtain a mixture; S3, the mixture is poured into an isostatic press under 120 MPa for compression molding, and dried to obtain a green body; S4, the green body is heat treated at 1600-1800℃ for 6-8h to obtain the final refractory material.

3. A method of producing a water vapor resistant refractory material for a glass melter as claimed in claim 2, characterized in that: The rotation speed of the raw materials in the ball mill in step S2 is 300 rpm, and the time is 1-3h.

4. A method of producing a water vapor resistant refractory material for a glass melting tank according to claim 3, characterized in that: After mixing uniformly in step S2, the mixture needs to be rested for 3-4h.

5. A method of making a water vapor resistant refractory material for a glass melter as defined in claim 4, wherein: The drying temperature in step S3 is 150℃, and the time is 6h.

6. A method of making a water vapor resistant refractory material for a glass melter as defined in claim 4, wherein: After drying in step S3, room temperature curing is required for 20-24h.

7. A method of making a water vapor resistant refractory material for a glass melter as defined in claim 4, wherein: The heating rate during the heat treatment in step S4 is 4℃ / min, and the cooling rate is 3℃ / min.

8. A method of making a water vapor resistant refractory material for a glass melter as defined in claim 4, wherein: The heat treatment process in step S4 needs to be carried out under nitrogen protection.

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